Viscous processing solution



United States Patent 3,238,043 VESCQUS PROCESSING SQLUTIUN Marilyn Levy, Red Bank, N.J., assignor to the United States of America as represented by the Secretary of the Army No Drawing. Filed July 6, 1961, Ser. No. 122,355 2 Claims. (Cl. 96-63) (Granted under Title 35, US. Code (1952), sec. 266) The invention described herein may be manufactured and used by or for the Government for governmental purposes, without the payment of any royalty thereon.

This invention relates to viscous processing solutions adapted for use by photographic processors and to separation systems utilizing the viscous processing solutions.

An object of the invention is to obtain a viscous processing solution that when sandwiched between a plastic or paper overlay and the gelatino-silver halide emulsion layer of a photosensitive film bearing a latent image will result in a separation system that can be rolled up as it is processed. Alternatively, where immediate scanning or reproduction after processing is desired, the object is to obtain a separation system wherein the viscous processing solution remains on the plastic or paper overlay when the overlay is stripped from the gelatino-silver halide layer of the photosensitive film bearing a latent image leaving the film free of viscous solution or marks of any kind.

It has been found that the foregoing objectives can be obtained by providing a viscous processing solution comprising a normally free-flowing solution of a resinous material and photographic processing agent admixed with a material incompatible with the resin solution. The viscous processing solution can be developing type, fixing type or combined developing-fixing type depending on the photographic processing agent selected. The viscous processing solution can be incorporated into a separation system by a number of methods.

One method involves the sandwiching of a viscous developing solution between a plastic or paper overlay and the gelatino-silver halide emulsion layer of a photosensitive film that has been exposed to light. When the plastic or paper coating is peeled oil, it takes with it, in a cohesive layer, the viscous processing solution leaving the developed gelatino-silver halide emulsion layer free of solution or marks of any kind. Alternatively, the sandwich type separation system can be rolled up as it is processed. Removal or inactivation of the residual silver halide can then be accomplished in a similar manner. That is, a viscous processing solution containing a fixer or stabilizing agent is sandwiched between the exposed and developed gelatino-silver halide emulsion layer of a photosensitive film and an overlay of plastic or paper. When this overlay is removed, the viscous processing solution sticks to the overlay rather than the gelatino-silver halide emulsion layer. One step processing can also be accomplished using a combined developer and fixer in the viscous processing solution.

Another method of incorporating the viscous processing solution into a separation system involves the application by painting, coating, spraying or the like of the processing solution directly onto the exposed gelatinosilver halide emulsion layer of a photosensitive film. The plastic or paper overlay is then placed over the viscous solution. When the overlay is pulled oil, the viscous solution forms a cohesive film that adheres preferentially to the plastic or paper overlay. This procedure can also be reversed and the viscous processing solution can be applied to the overlay. The coated overlay is then pressed in contact with the film until the desired processing is accomplished. When the overlay is peeled off, the viscous material will again preferentially stick to the overlay.

The separation systems utilizing the viscous processing solutions are based on the fact that free flowing colloidal solutions of resins will form a cohesive rubbery gel when mixed with other materials that are incompatible with the resin solution. The viscous processing solutions of the lnvention are especially useful for photographic processing in moving vehicles as for example, in airplanes in flight as spillage of processing solutions is greatly reduced or eliminated. Furthermore, there is no necessity of washing the film free of the processing material in immediate scanning as the stripping operation leaves the film clean and free of viscous solution or marks of any kind. The viscous processing solutions and separation systems using the viscous processing solutions can also be adapted to conventional film processing methods.

Some preferred embodiments of this invention are shown in the following examples.

Example 1.-A viscous fixing solution is prepared from the following ingredients- Ingredient: Amount A. Sodium polyacrylate (12.5% in water) cc 300 B. Ammonium thiocyanate grams 110 C. Lauryl trimethyl ammonium chloride (50% in isopropanol) -cc 6-20 When C above is added to the free-flowing solution of A and B above, there results a viscous fixing solution of a slightly rubbery texture. The solution is then coated onto the gelatino-silver halide emulsion layer of a photosensitive film bearing a latent image, and the viscous fixing solution is covered with a carrier or protective layer which may be cloth, paper, plastic, etc. This separation system may be rolled up the protective layer stripped from the film leaving the film free of viscous solution or marks of any kind.

Example 2.A viscous fixing solution is prepared from the following ingredients.

Ingredient: Amount A. Polyacrylamide (15% in water) cc 300 B. Lauryl trimethyl ammonium chloride (50% in isopropanol) cc 3 C. Polyvinyl pyrrolidone (45% in water) cc 10 D. Alum grarns 10 E. Ammonium thiocyanate or ammonium thiosulfate do When B and C above are added to the free-flowing solution from A, D, and E above, a viscous fixing solution results as in Example 1.

Example 3.--A viscous developing solution is prepared from the following ingredients.

Ingredient: Amount A. Sodium acrylate cc 300 B. Sodium sulfite grams 30 C. Hydroquinone c do 15 D. Sodium hydroxide do 10 E. Phenidone do 3 F. Polyvinyl pyrrolidone (45% in water) cc 15 The Example 4.A viscous fixing solution is prepared from the following ingredients.

Ingredients: Amount, grams A. Sodium carboxy methyl cellulose 10-30 B. Methyl cellulose -30 C. Sodium thiosulphate 50-250 D. Sodium sulfite 5-15 E. Water 50-1000 When B above is added to the free-flowing solution of A, C, D, and E above, there results a viscous fixing solution of a slightly rubbery texture.

In the above example, it is possible to reverse the arrangement of resinous material and material incompatible with the resin solution. Thus, it is possible to start with a resin solution of methyl cellulose and photographic processing agent, and admix therewith the sodium carboxy methyl cellulose as the incompatibilizing material.

Example 5.A viscous developing solution is prepared from the following ingredients.

Ingredient: Amount, grams A. Sodium carboxy methyl cellulose -30 B. Polyvinyl alcohol 5-30 C. Sodium sulfite 10-100 D. Hydroquinone 10-15 E. Sodium hydroxide 10-35 F. Potassium bromide 20-30 G. Water 100-1000 When B above is added to the free-flowing solution of A, C, D, E, F, and G, there results a viscous developing solution of a slightly rubbery texture. This solution can be sandwiched between the exposed film and a plastic or cloth overlay with the same results as in Example 1. Furthermore, the polyvinyl alcohol can be the resinous material and the sodium canboxy methyl cellulose, the incompatibilizing material.

Example 6.A viscous developing solution is prepared from the following ingredients.

Ingredient: Amount, grams A. Sodium carboxy methyl cellulose 10-30 B. Tri ethyl phosphate 5-30 C. Methyl-para-aminophenol 3 D. Sodium sulfite 100 E. Hydroquinone 10 F. Sodium carbonate 40 G. Potassium bromide 3 H. Water 100-1000 When B above is added to the free-flowing solution from A, C, D, E, F, G, and H, there results a viscous developing solution of a slightly rubbery texture adapted for use in the separation systems of the invention.

Example 7.A viscous fixing solution is prepared from the following ingredients.

Ingredient: Amount, grams A. Sodium carboxy methyl cellulose 10-30 B. Glycollated melamine formaldehyde resin 5-30 C. Guanidine thiocyanate 30-250 D. Water 100-1000 When B above is added to the free-flowing solution formed from A, C, and D above, there results a viscous fixing solution adapted for use in the separation systems of the invention.

Example 8.-A viscous fixing solution is prepared from the following ingredients.

Ingredient: Amount, grams A. Sodium carboxy methylv cellulose 10-30 B. Glycollated urea formaldehyde resin 5-30 C. 2-diethylaminoethanethiol 10-500 D. Water 100-1000 When B above is added to the free-flowing solution formed from A, C, and D above, there results a viscous fixing solution adapted for use in the separation systems of the invention.

Example 9.-A combined viscous developing and fixing solution is prepared from the following ingredients.

Ingredient: Amount, grams A. Water soluble high molecular weight polymers of ethylene oxide 1-10 B. Alkyl ether of polyethylene glycol 0.01-5 C. Sodium sulfite 60 D. Hydroquinone 30 E. Sodium hydroxide 25 F. Phenidone 3 G. Sodium thiosulfate -250 H. Water 1000 When B above is added to the free-flowing solution formed from A, C, D, E, F, G, and H above, there results Ingredient: Amount, grams A. Hydroxy ethyl cellulose 1-15 B. Methyl cellulose l-10 C. Methyl-para-aminophenol 2 D. Sodium sulfite 50 E. Hydroquinone 2 F. Sodium metaborate 20 G. Potassium bromide 1 H. Water 100-1000 When B above is added to a free-flowing solution from A, C, D, E, F, G, and H, there results a viscous developing solution of a slightly rubbery texture. In this example, in lieu of using methyl cellulose as the incompatibilizing material, 1-10 grams of either polyvinyl alcohol or zein can be used.

Example 11.A viscous fixing solution is prepared from the following ingredients.

Ingredient: Amount, grams A. Polyvinylpyrrolidone 1-50 B. Bone glue 0.05-5 C. Potassium iodide 50-200 D. Water 100-500 When B above is added to the free-flowing solution formed A, C, and D above, there results a viscous fixing solution of a slightly rubbery texture. In lieu of the use of bone glue as the incompatibilizing material, there may be used 0.01-10 grams of sodium alkylnaphthalene sulfonate or 0.01-5 grams of lecithin.

It is intended that the foregoing disclosure be considered for illustrative purposes only and not in limitation of the invention as hereinafter claimed.

What is claimed is:

1. A viscous processing solution in the form of a cohesive rubbery gel adapted for use by photographic processors comprising the admixture of a resinous solution of materials selected from the group consisting of sodium polyacrylate and lauryl trimethyl ammonium chloride, sodium polyacrylate and polyvinyl pyrrolidone, sodium polyacrylate and glycollated melamine formaldehyde resin, sodium polyacrylate and glycollated urea formaldehyde resin, sodium polyacrylate and alkyl ether of polyethylene glycol, sodium polyacrylate and sodium heptadecyl sulfate, sodium polyacrylate and sodium methyl oleoyl taurate, sodium polyacrylate and dipropylene glycol, sodium polyacrylate and polypropylene glycol, sodium polyacrylate and butyl phthalyl butyl glycolate, sodium polyacrylate and zein, sodium polyacrylate and sodium alkylnaphthalene sulfonate, sodium polyacrylate and lecithin, polyacrylamide and lauryl trimethyl ammonium chloride, polyacrylamide and polyvinyl pyrrolidone, polyacrylamide and glycollated melamine formaldehyde resin, polyacrylamide and glycollated urea formaldehyde resin, polyacrylamide and alkyl ether of polyethylene glycol, polyacrylamide and sodium heptadecyl sulfate, polyacrylamide and sodium methyl oleoyl taurate, polyacrylamide and dipropylene glycol, polyacrylamide and polypropylene glycol, polyacrylamide and butyl phthalyl butyl glycolate, polyacrylamide and zein, polyacrylamide and sodium alkylnaphthalene sulfonate, polyacrylamide and lecithin, sodium acrylate and lauryl trimethyl ammonium chloride, sodium acrylate and polyvinyl pyrrolidone, sodium acrylate and glycollated melamine formaldehyde resin, sodium acrylate and glycollated urea formaldehyde resin, sodium acrylate and alkyl ether of polyethylene glycol, sodium acrylate and sodium heptadecyl sulfate, sodium acrylate and sodium methyl oleoyl taurate, sodium acrylate and dipropylene glycol, sodium acrylate and polypropylene glycol, sodium acrylate and butyl phthalyl butyl glycolate, sodium acrylate and zein, sodium acrylate and sodium alkylnaphthalene sulfonate, sodium acrylate and lecithin, water soluble high molecular weight polymers of ethylene oxide and lauryl trimethyl ammonium chloride, water soluble high molecular weight polymers of ethylene oxide and polyvinyl pyrrolidone, water soluble high molecular weight polymers of ethylene oxide and glycollated melamine formaldehyde resin, Water soluble high molecular Weight polymers of ethylene oxide and glycollated urea formaldehyde resin, water soluble high molecular Weight polymers of ethylene oxide and alkyl ether of polyethylene glycol, Water soluble high molecular Weight polymers of ethylene oxide and sodium heptadecyl sulfate, Water soluble high molecular Weight polymers of ethylene oxide and sodium methyl oleoyl taurate, water soluble high molecular Weight polymers of ethylene oxide and dipropylene glycol, water soluble high molecular weight polymers of ethylene oxide and polypropylene glycol, Water soluble high molecular weight polymers of ethylene oxide and butyl phthalyl butyl glycolate, Water soluble high molecular Weight polymers of ethylene oxide and zein, Water soluble high molecular Weight polymers of ethylene oxide and sodium alkylnaphthalene sulfonate, water soluble high molecular Weight polymers or ethylene oxide and lecithin, With a photographic processing agent selected from at least one member of the group consisting of developing agents, fixing agents, and a combination of developing and fixing agents.

2. A separation system adapted for use in photographic processing comprising a photosensitive sheet of an exposed gelatino-silver halide emulsion layer and a protective overlay for said photosensitive sheet, said photosensitive sheet and said protective overlay being separated by a viscous processing solution in the form of a cohesive rubbery gel comprising the admixture of a resinous solution of materials selected from the group consisting of sodium polyacrylate and lauryl trimethyl ammonium chloride, sodium polyacrylate and polyvinyl pyrrolidone, sodium polyacrylate and glycollated melamine formaldehyde resin, sodium polyacrylate and glycollated urea formaldehyde resin, sodium polyacrylate and alkyl ether of polyethylene glycol, sodium polyacrylate and sodium heptadecyl sulfate, sodium polyacrylate and sodium methyl oleoyl taurate, sodium polyacrylate and dipropylene glycol, sodium polyacrylate and polypropylene glycol,

sodium polyacrylate and butyl phthalyl butyl glycolate, sodium polyacrylate and zein, sodium polyacrylate and sodium alkylnaphthalene sulfonate, sodium polyacrylate and lecithin, polyacrylamide and lauryl trimethyl ammonium chloride, polyacrylamide and polyvinyl pyrrolidone, polyacrylamide and glycollated melamineformaldehyde resin, polyacrylamide and glycollated urea formaldehyde resin, polyacrylamide and alkyl ether of polyethylene glycol, polyacrylamide and sodium heptadecyl sulfate, polyacrylamide and sodium methyl oleoyl taurate, polyacrylamide and dipropylene glycol, polyacrylamide and polypropylene glycol, polyacrylamide and butyl phthalyl butyl glycolate, polyacrylamide and zein, polyacrylamide and sodium alkylnaphthalene sulfonate,

polyacrylamide and lecithin, sodium acrylate and lauryl trimethyl ammonium chloride, sodium acrylate and polyvinyl pyrrolidone, sodium acrylate and glycollated melamine formaldehyde resin, sodium acrylate and glycollated urea formaldehyde resin, sodium acrylate and alkyl ether of polyethylene glycol, sodium acrylate and sodium heptadecyl sulfate, sodium acrylate and sodium methyl oleoyl turate, sodium acrylate and dipropylene glycol, sodium acrylate and polypropylene glycol, sodium acrylate and butyl phthalyl butyl glycolate, sodium acrylate and zein, sodium acrylate and sodium alkylnaphthalene sulfonate, sodium acrylate and lecithin, water soluble high molecular weight polymers of ethylene oxide and lauryl trimethyl ammonium chloride, water soluble high molecular Weight polymers of ethylene oxide and polyvinyl pyrrolidone, water soluble high molecular Weight polymers of ethylene oxide and glycollated melamine formaldehyde resin, water soluble high molecular Weight polymers of ethylene oxide and glycollated urea formaldehyde resin, water soluble high molecular Weight polymers of ethylene oxide and alkyl ether of polyethylene glycol, Water soluble high molecular weight polymers of ethylene oxide and sodium heptadecyl sulfate, water soluble high molecular weight polymers of ethylene oxide and sodium methyl oleoyl turate, Water soluble high molecular weight polymers of ethylene oxide and dipropylene glycol, Water soluble high molecular Weight polymers of ethylene oxide and polypropylene glycol, Water soluble high molecular weight polymers of ethylene oxide and butyl phthalyl butyl glycolate, water soluble high molecular weight polymers of ethylene oxide and zein, water soluble high molecular Weight polymers of ethylene oxide and sodium alkylnaphthalene sulfonate, water soluble high molecular Weight polymers of ethylene oxide and lecithin, With a photographic processing agent selected from at least one member of the group consisting of developing agents, fixing agents, and a combination of developing and fixing agents.

References Cited by the Examiner UNITED STATES PATENTS 2,603,565 7/1952 Land 96-61 2,616,807 11/1952 Land 9629 2,964,405 12/1960 Talbot et al. 96113 3,022,169 2/1962 Heckelmann et al. 9667 3,030,270 4/1962 Land 9629 3,121,060 2/1964 Duane 252-56 FOREIGN PATENTS 837,972 6/ 1960 Great Britain.

NORMAN G. TORCHIN, Primary Examiner.

HAROLD N. BURSTEIN, Examiner.

W. C. GILLIS, A. D. RICCI, C. DAVIS,

Assistant Examiners, 

1. A VISCOUS PROCESSING SOLUTION IN THE FORM OF A COHESIVE RUBBERY GEL ADAPTED FOR USE BY PHOTOGRAPHIC PROCESSORS COMPRISING THE ADMIXTURE OF A RESINOUS SOLUTION OF MATERIALS SELECTED FROM THE GROUP CONSISTING OF SODIUM POLYACRYLATE AND LAURYL TRIMETHYL AMMONIUM CHLORIDE, SODIUM POLYACRYLATE AND POLYVINYL PYRROLIDONE, SODIUM POLYACRYLATE AND GLYCOLLATED MELAMINE FORMALDEHYDE RESIN, SODIUM POLYACRYLATE AND GLYCOLLATED UREA FORMALDEHYDE RESIN, SODIUM POLYACRYLATE AND ALKYL ETHER OF POLYETHYLENE GLYCOL, SODIUM POLYACRYLATE AND SODIUM HEPTADECYL SULFATE, SODIUM POLYACRYLATE AND SODIUM METHYL OLEOYL TAURATE, SODIUM POLYACYLATE AND DIPROPYLENE GLYCOL, SODIUM POLYACRYLATE AND POLYPROPYLENE GLYCOL, SODIUM POLYACRYLATE AND BUTYL PHTHALYL BUTYL GLYCOLATE, SODIUM POLYACRYLATE AND ZEIN, SODIUM POLYACRYLATE AND SODIUM ALKYLNAPHTHALENE SULFONATE, SODIUM POLYACRYATE AND LECITHIN, POLYACRYLAMIDE AND LAURYL TRIMETHYL AMMONIUM CHLORIDE, POLYACRYLAMIDE AND POLYVINYL PYRROLIDONE, POLYACRYLAMIDE AND GLYCOLLATED UREA FORMALDEHYDE RESIN, POLYACRYLAMIDE AND SODIUM HEPTADECYL SULFATE, POLYACRYLAMIDE AND SODIUM METHYL OLEOYL TAURATE, POLYACRYLAMIDE AND DIPROPYLENE GLYCOL, POLYACRYLAMIDE AND POLYPROPYLENE GLYCOL, POLYACRYLAMIDE AND BUTYL PHTHALYL BUTYL GLYCOLATE, POLYACRYLAMIDE AND ZEIN, POLYACRYLAMIDE AND LECITHIN, SODIUM ACRYLATE AND LAURYL TRIMETHYL AMMONIUM CHLORIDE, SODIUM ACRYLATE AND POLYVINYL PYRROLIDONE, SODIUM ACRYLATE AND GLYCOLLATED MELAMINE FORMALDEHYDE RESIN, SODIUM ACRYLATE AND GLYCOLLATED UREA FORMALDEHYDE RESIN, SODIUM ACRYLATE AND ALKYL ETHER OF POLYETHYLENE GLYCOL, SODIUM ACRYLATE AND SODIUM HEPTADECYL SULFATE, SODIUM ACRYLATE AND SODIUM METHYL OLEOYL TAURATE, SODIUM ACRYLATE AND SODIUM METHYL OLEOYL TAURATE, SODIUM ACRYLATE AND DIPROPYLENEN GLYCOL, SODIUM ACRYLATE AND POLYPROPYLENE GLYCOL, SODIUM ACRYLATE AND BUTYL PHTHALYL BUTYL GLYCOLATE, SODIUM ACRYLATE AND ZEIN, SODIUM ACRYLATE AND SODIUM ALKYLNAPHTH ALENE SULFONATE, SODIUM ACRYLATE AND LECITHIN, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND LAURYL TRIMETHYL AMMONIUM CHLORIDE, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND POLYVINYL PYRROLIDONE, WATER SOLUBLE HIGH MOLECUAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND GLYCOLLATED MELAMINE FORMALDEHYDE RESIN, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND GLYCOLLATED UREA FORMALDEHYDE RESIN, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND ALKYL ETHER OF POLYETHYLENE GLYCOL, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND SODIUM HEPTADECYL SULFATE, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND SODIUM METHYL OLEOYL TAURATE, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND DIPROPYLENE GLYCOL, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND POLYPROPYLENE GLYCOL, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND BUTYL PHTHALYL BUTYL GLYCOLATE, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND ZEIN, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OF ETHYLENE OXIDE AND SODIUM ALKYLNAPHTHALENE SULFONATE, WATER SOLUBLE HIGH MOLECULAR WEIGHT POLYMERS OR ETHYLENE OXIDE AND LECITHIN, WITH A PHOTOGRAPHIC PROCESSING AGENT SELECTED FROM AT LEAST ONE MEMBER OF THE GROUP CONSISTING OF DEVELOPING AGENTS, FIXING AGENTS, AND A COMBINATION OF DEVELOPING AND FIXING AGENTS. 